JP5857279B2 - Self-lubricating coating and method for producing self-lubricating coating - Google Patents
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- 238000000576 coating method Methods 0.000 title claims description 64
- 239000011248 coating agent Substances 0.000 title claims description 58
- 238000004519 manufacturing process Methods 0.000 title description 2
- 229910052751 metal Inorganic materials 0.000 claims description 46
- 239000002184 metal Substances 0.000 claims description 46
- 239000000314 lubricant Substances 0.000 claims description 37
- 150000002894 organic compounds Chemical class 0.000 claims description 33
- 239000003792 electrolyte Substances 0.000 claims description 10
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 8
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 229920002521 macromolecule Polymers 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052745 lead Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 230000001050 lubricating effect Effects 0.000 description 30
- 229940125782 compound 2 Drugs 0.000 description 13
- 125000000524 functional group Chemical group 0.000 description 13
- 239000008151 electrolyte solution Substances 0.000 description 11
- 239000002105 nanoparticle Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000000412 dendrimer Substances 0.000 description 5
- 229920000736 dendritic polymer Polymers 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 230000002411 adverse Effects 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- -1 silicon Chemical compound 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
- C10M125/04—Metals; Alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
- H01R13/00—Details of coupling devices of the kinds covered by groups H01R12/70 or H01R24/00 - H01R33/00
- H01R13/02—Contact members
- H01R13/03—Contact members characterised by the material, e.g. plating, or coating materials
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Electrochemistry (AREA)
- Inorganic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Lubricants (AREA)
- Electroplating Methods And Accessories (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Paints Or Removers (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Description
本発明は、摩耗によって解放可能な潤滑剤が埋め込まれた金属層を構成するコーティングに関する。本発明は、さらに、少なくとも所定部分において塗布されたコーティングを備えた自己潤滑性部品、コーティングおよび自己潤滑性部品の生産方法、イオンまたは錯体として溶解した金属の少なくとも１つの形態および少なくとも1つの潤滑剤を含むコーティング電解質に関する。 The present invention relates to a coating comprising a metal layer embedded with a lubricant that can be released by wear. The invention further provides a self-lubricating part with a coating applied at least in a predetermined part, a method for producing the coating and the self-lubricating part, at least one form of metal dissolved as an ion or complex and at least one lubricant It relates to the coating electrolyte containing.
材料の表面におけるコーティングは、物理的特性、電気的特性、および／または、化学的特性に影響を与えることが知られている。表面は、例えば、表面コーティングが摩耗からの機械的保護を与え、耐食性を示し、生体適合性および／または導電性の向上性を有するなどの表面技術加工で補助することで取り扱うことが可能である。 Coatings on the surface of a material are known to affect physical properties, electrical properties, and / or chemical properties. The surface can be handled, for example, with the aid of surface engineering processes such that the surface coating provides mechanical protection from wear, exhibits corrosion resistance, and has improved biocompatibility and / or conductivity. .
プラグイン接続コンタクトおよびプレスインコネクタにおいて、トライボロジーおよび摩耗は、多くの場合、可能な作動数を決定し、適切な動作を確実にする。プラグイン接続コンタクトおよびプレスイン接続の部品の外側にオイルまたは潤滑油を塗布することによる摩擦の低減すなわち摩耗の低減は、制限された作動においてのみ効果的であり、長期的なものではなく、化学的に変化してしまう可能性もある。 In plug-in connection contacts and press-in connectors, tribology and wear often determine the number of possible actuations and ensure proper operation. Friction or wear reduction by applying oil or lubricating oil on the outside of plug-in connection and press-in connection parts is effective only in limited operation, not long-term, chemical May change.
それゆえに、摩耗抵抗の増強が長持ちするようにコーティングを得ることが望ましい。 Therefore, it is desirable to obtain a coating so that the increased wear resistance lasts.
ＰＣＴ国際公開２００８／１２２５７０号明細書には、例えば、少なくとも１種のマトリックス金属を備えたマトリックスを備えるプラグの電気的導電部などの部品のためのコーティングが開示されている。５０ｎｍよりも小さい平均サイズであり、かつ、各々が少なくとも１つの機能キャリアを備えるナノ粒子が、金属マトリックス中に埋め込まれる。機能キャリアは、所望状態で金属マトリックスに影響を与えるように機能する。例えば、機能キャリアとしての金属は、コーティングの導電性を変化させる。シリコンカーバイド、窒化ホウ素、酸化アルミニウムおよび／またはダイヤモンドなどの特定の硬質材料で形成された機能キャリアは、金属マトリックスの硬度を増強し、コーティングされた材料の摩耗特性を改善する。 PCT WO 2008/122570 discloses coatings for parts such as, for example, electrically conductive parts of plugs comprising a matrix with at least one matrix metal. Nanoparticles with an average size of less than 50 nm and each comprising at least one functional carrier are embedded in the metal matrix. The functional carrier functions to affect the metal matrix in the desired state. For example, a metal as a functional carrier changes the conductivity of the coating. Functional carriers formed of certain hard materials such as silicon carbide, boron nitride, aluminum oxide and / or diamond enhance the hardness of the metal matrix and improve the wear properties of the coated material.
付加的な潤滑剤の注入が不要な部品の摩耗低減コーティングは、例えば欧州特許公開０７４８８８３号明細書などで知られている。本文献のコーティングは、摩耗減少物質が埋め込まれたナノ粒子が不均一に拡散した状態で導入された金属層によって区別される。このナノ粒子は、例えば、Ａｌ２Ｏ３，ＺｒＯまたはＴｉＯ２からなり、その表面に石鹸化合物を備えてもよい。 A wear-reducing coating on parts that does not require additional lubricant injection is known, for example, from EP 0 488 883. The coatings in this document are distinguished by a metal layer introduced in a non-uniformly diffused state of nanoparticles embedded with wear-reducing substances. The nanoparticles are made of, for example, Al 2 O 3 , ZrO or TiO 2 and may have a soap compound on the surface thereof.
欧州特許公開０７４８８８３号明細書およびＰＣＴ国際公開２００８／１２２５７０号明細書のコーティングは、表面コーティングの特性に影響を与える実際の機能キャリアがキャリアと結合しつつ金属層中に埋め込まれるという欠点がある。この結合過程は付加的なステップとなり、材料消費量を増加させ、コーティングがより高コストとなることになる。 The coatings of EP 0 748 883 and PCT WO 2008/122570 have the disadvantage that the actual functional carriers that influence the properties of the surface coating are embedded in the metal layer while bonded to the carrier. This bonding process is an additional step, increasing material consumption and making the coating more expensive.
それゆえに、本発明の目的は、耐摩耗性が改善されたコーティングを簡単な構造で経済的に生産することにある。 The object of the present invention is therefore to economically produce coatings with improved wear resistance with a simple structure.
本発明によれば、はじめに言及したコーティングおよび上述のコーティング電解質は、金属層に埋め込まれる潤滑剤が少なくとも１つが分岐した有機化合物からなることで、その目的が達成される。 According to the present invention, the purpose of the coating mentioned above and the above-described coating electrolyte is achieved when the lubricant embedded in the metal layer is made of an organic compound having at least one branch.
本発明によれば、はじめに言及したコーティングの生産方法は、
ａ）少なくとも１つが分岐した有機化合物からなる少なくとも１つの潤滑剤をイオンまたは錯体として溶解された少なくとも１種の金属を含む電解質溶液に加える工程と、
ｂ）部品へのコーティング材として、前記電解質溶液から前記溶解された金属および前記潤滑剤を塗布する工程と、によってその目的が達成される。
According to the present invention, the method of producing the coating mentioned at the beginning is
a) adding at least one lubricant comprising at least one branched organic compound to an electrolyte solution comprising at least one metal dissolved as an ion or complex;
b) The object is achieved by applying the dissolved metal and the lubricant from the electrolyte solution as a coating material for the parts.
本発明において、金属層に埋め込まれた有機化合物は、本発明のコーティングが剥離や摩耗に晒される間、コーティングの表面において部分的に露出する潤滑剤であり、そこで摩耗を減少する潤滑膜を形成する。本発明では、欧州特許公開０７４８８８３号明細書およびＰＣＴ国際公開２００８／１２２５７０号明細書に記載の無機物のナノ粒子などのようなキャリア要素は、必要とされない。このため、機能キャリア、すなわち、ＰＣＴ国際公開２００８／１２２５７０号明細書に記載の金属や欧州特許公開０７４８８８３号明細書に記載の石鹸化合物などをキャリア粒子と結合させる別工程を省略できる。 In the present invention, the organic compound embedded in the metal layer is a lubricant that is partially exposed on the surface of the coating while the coating of the present invention is exposed to peeling and wear, where it forms a lubricating film that reduces wear. To do. In the present invention, carrier elements such as inorganic nanoparticles described in European Patent Publication No. 0748883 and PCT International Publication No. 2008/122570 are not required. For this reason, the separate process which combines the functional carrier, ie, the metal described in PCT International Publication No. 2008/122570, the soap compound described in European Patent Publication No. 074883, and the like with carrier particles can be omitted.
本発明によるコーティングの所望の潤滑効果は、潤滑性有機化合物の最小の単原子中間層または二層の接触部において、予め達成されるので、本発明によるコーティングの耐摩耗性は、複合的に増強される。よって、必要となる層厚も小さくして、原材料の消費低減およびコスト削減とすることができる。 Since the desired lubricating effect of the coating according to the invention is achieved in advance at the smallest monoatomic intermediate layer or bilayer contact of the lubricating organic compound, the wear resistance of the coating according to the invention is compounded Is done. Therefore, the required layer thickness can be reduced, and the consumption of raw materials and the cost can be reduced.
有機化合物とは、無機化学とされる例外を除く、全ての炭素化合物であり、例えばシリコンなどのカーボンを殆ど含んでいない例えばカーバイド、それ自身および他の元素、例えば、Ｈ，Ｎ，Ｏ，Ｓｉ，Ｂ，Ｆ，Ｃｌ，Ｂｒ，Ｓ，Ｐなどまたはこれら元素の組み合わせを有するものを挙げることができる。 Organic compounds are all carbon compounds with the exception of inorganic chemistry, for example, carbides that contain little carbon such as silicon, for example, themselves and other elements such as H, N, O, Si. , B, F, Cl, Br, S, P, etc., or those having a combination of these elements.
本発明による解決によって、各々が互いに独立する配置の数をさらに改善することができる。これら配置およびこれらに関連する利点については、後述で簡潔に説明する。 The solution according to the invention makes it possible to further improve the number of arrangements each independent of each other. These arrangements and their associated advantages are briefly described below.
好適には、有機化合物は、三次元分子構造を有する。三次元であるゆえに嵩張らない分子構造により、潤滑剤分子が電解質溶液中により均一に拡散し、凝集や塊となってしまう不具合が低減される。それゆえに、電解質溶液中およびコーティング中に潤滑剤を特に均一拡散とさせることも可能となる。しかしながら、アプリケーションによっては、ほぼ鎖状または平面分子構造（すなわち有機化合物における原子配置が実質的に直線状またはシート状）を有する有機化合物を用いることも可能である。 Preferably, the organic compound has a three-dimensional molecular structure. Due to the three-dimensional molecular structure which is not bulky, the problem that the lubricant molecules diffuse more uniformly in the electrolyte solution and become aggregates or lumps is reduced. Therefore, it is possible to make the lubricant particularly uniformly diffused in the electrolyte solution and in the coating. However, depending on the application, it is also possible to use an organic compound having a substantially chain-like or planar molecular structure (that is, the atomic arrangement in the organic compound is substantially linear or sheet-like).
好適な態様において、有機化合物は、本願において減摩分子または潤滑分子としても後述されるが、マクロ分子である。”マクロ分子”は、同じまたは異なる原子または原子群からなり、分子間の最大空間次元の距離に沿って少なくとも１５分子を有する分子のことを称する。この種のマクロ分子潤滑剤は、ポリマーを含み、幅広い使用領域で用いることができ、対応するアプリケーションに最適化されたものを選択できるという利点がある。マクロ分子とその鎖状部がコポリマー、混合ポリマーおよびブロック重合体を含み、これらはコンタクトに備えられた層システムの潤滑特性を有し、かつ、電気特性に悪影響を与えないようして選択されることだけに注意しなければならない。さらには、潤滑剤として使用される有機化合物は、当然、有機化合物が悪影響を与えないコーティングを生産するために、電解質溶液中で化学的に安定であるべきである。 In a preferred embodiment, the organic compound is a macromolecule, which is also described herein as an anti-friction or lubricating molecule. A “macromolecule” refers to a molecule that consists of the same or different atoms or groups of atoms and that has at least 15 molecules along the maximum spatial dimension distance between the molecules. This type of macromolecular lubricant has the advantage that it contains a polymer, can be used in a wide range of applications, and can be selected to be optimized for the corresponding application. Macromolecules and their chains include copolymers, mixed polymers and block polymers, which are selected to have the lubricating properties of the layer system provided in the contact and not adversely affect the electrical properties You just have to be careful. Furthermore, the organic compound used as a lubricant should of course be chemically stable in the electrolyte solution in order to produce a coating in which the organic compound does not adversely affect.
有機化合物は、約１０ｎｍ、好適には上限約３ｎｍの最大空間次元距離を有すると特によい潤滑特性を有する。特にこの大きさのオーダーの分子の潤滑性は、トンネル効果によって導電的であり、導電性のためのコーティングに用いることも可能である。本願明細書において、”最大空間次元”という言葉は、空間軸に沿っての分子の最大延伸距離（例えば、球状または平面形状の潤滑剤では直径）を示す。有機化合物としては、最大空間次元に沿って、約２００原子、好適には約６０原子の最大鎖長にほぼ対応する。 The organic compound has particularly good lubricating properties with a maximum spatial dimension distance of about 10 nm, preferably an upper limit of about 3 nm. In particular, the lubricity of molecules of this size order is conductive by the tunnel effect and can also be used for coatings for conductivity. As used herein, the term “maximum spatial dimension” refers to the maximum stretch distance of a molecule along the spatial axis (eg, the diameter for a spherical or planar lubricant). Organic compounds approximately correspond to a maximum chain length of about 200 atoms, preferably about 60 atoms, along the maximum spatial dimension.
本発明に用いられる潤滑分子の比較的低い空間次元（５０ｎｍの大きさのオーダーより小さい）のために、使用されるナノ粒子のコーティングにおいて、コーティングにおける金属粒子サイズが、潤滑分子自体のナノスケール範囲まで小さくすることが可能である。 Due to the relatively low spatial dimension (less than the order of 50 nm) of the lubricating molecules used in the present invention, in the coating of nanoparticles used, the metal particle size in the coating is in the nanoscale range of the lubricating molecule itself. It is possible to make it smaller.
潤滑性の有機化合物は、特に樹枝状構造、すなわち、多分岐かつ著しく分岐させる態様の構造であってもよい。多分岐かつ著しい分岐は、対称形状でも非対称形状であってもよい。潤滑分子として樹枝状基質およびポリマーは、特にナノ粒子において低粘度でナノ構造を形成する傾向であると電解質溶液中に良好に拡散する点で特によい。 The lubricious organic compound may in particular have a dendritic structure, i.e. a multi-branched and highly branched structure. The multi-branch and significant branch may be symmetric or asymmetric. Dendritic substrates and polymers as lubricating molecules are particularly good in that they tend to diffuse well into the electrolyte solution, especially when they tend to form nanostructures with low viscosity in the nanoparticles.
潤滑剤の埋め込み度を増加させるために、有機化合物は、金属層の金属への親和性を有する少なくとも１つの官能基を備えてもよい。この官能基によって、潤滑分子を、付着工程中に金属層の浅い部分に配置されても、金属層方向へ移動させ、金属層中に沈殿させる。原則的には、金属層への官能基の親和性は、潤滑剤の埋め込みまたは沈殿を促進させるために、電解質溶液の溶媒よりも高い。 In order to increase the degree of embedding of the lubricant, the organic compound may comprise at least one functional group having an affinity for the metal of the metal layer. Due to this functional group, even if the lubricating molecules are arranged in the shallow part of the metal layer during the deposition process, they move toward the metal layer and precipitate in the metal layer. In principle, the affinity of the functional group to the metal layer is higher than the solvent of the electrolyte solution in order to promote the embedding or precipitation of the lubricant.
官能基の金属親和性は拡散層中（すなわちコーティング表面に直近した箇所）だけに効果があるので、潤滑分子の凝集すなわち潤滑分子によって金属層が完全に覆われるようなことはなくなる。電解質溶液中の潤滑分子の凝集リスクを除外するために、有機化合物中に官能基を与え、電解質溶液中の個々の潤滑分子を相互反発させる。この官能基は好適には端部、すなわち鎖状部の端部または鎖状部の各分岐部に配置される。 Since the metal affinity of the functional group is effective only in the diffusion layer (that is, the portion closest to the coating surface), the metal layer is not completely covered by the aggregation of the lubricating molecules, that is, the lubricating molecules. In order to eliminate the risk of aggregation of the lubricating molecules in the electrolyte solution, functional groups are provided in the organic compound to repel individual lubricating molecules in the electrolyte solution. This functional group is preferably arranged at the end, ie at the end of the chain or at each branch of the chain.
対応官能基が有機化合物の表面に配置されると、金属層への親和性のためと潤滑分子の相互反発のための両方に好適である。官能基は、潤滑分子の外側に露出し、それゆえに、潤滑分子が電解質溶液中で金属層とまたは互い同士が接触するように配置される。 When the corresponding functional group is arranged on the surface of the organic compound, it is suitable both for the affinity for the metal layer and for the mutual repulsion of the lubricating molecules. The functional groups are exposed to the outside of the lubricating molecules and are therefore arranged such that the lubricating molecules are in contact with the metal layer or with each other in the electrolyte solution.
特に好適な実施形態において、官能基は、金属への高親和性を有し、かつ、分極によって潤滑分子の相互反発を確実にするので、チオール基であってもよい。 In a particularly preferred embodiment, the functional group may be a thiol group because it has a high affinity for the metal and ensures reciprocal repulsion of the lubricating molecules by polarization.
本発明において、官能基の選択は、コーティングの金属層にも依存する。金属層は、Ｃｕ，Ｎｉ，Ｃｏ，Ｆｅ，Ａｇ，Ａｕ，Ｐｄ，Ｐｔ，Ｒｈ，Ｗ，Ｃｒ，Ｚｎ，Ｓｎ，Ｐｂおよびこれらの合金の群から選択されると好適である。特には、ＡｕまたはＡｇからなる金属層は、これら金属へのチオール基の高親和性のために、チオール基を有する潤滑分子に対して効果的に相互作用する。 In the present invention, the functional group selection also depends on the metal layer of the coating. The metal layer is preferably selected from the group of Cu, Ni, Co, Fe, Ag, Au, Pd, Pt, Rh, W, Cr, Zn, Sn, Pb and alloys thereof. In particular, metal layers made of Au or Ag effectively interact with lubricating molecules having thiol groups because of the high affinity of thiol groups for these metals.
本発明に係るコーティング電解質には、例えば本発明におけるａ）の段階で生産されるなどすることで、少なくとも１種の金属イオンおよび本発明のコーティング中に埋め込まれる上述の実施形態のうちの１つにおける少なくとも１種の有機化合物からなる潤滑剤を含ませる。 The coating electrolyte according to the present invention includes at least one metal ion and one of the above-described embodiments embedded in the coating of the present invention, for example, by being produced in the step a) of the present invention. And a lubricant composed of at least one organic compound.
さらに、本発明は、上述の実施形態のコーティングが少なくとも一部分に塗布される自己潤滑性部品に関する。本発明における自己潤滑性部品において、コーティングは、電気コンタクトの表面に付着されると好適であり、本発明のコーティングによって耐摩耗性が増強するために、より薄い層で良好なコンタクト接触を提供することが可能となり、対応するコンタクトの小型化および簡素化に貢献し、低重量化および原材料の消費量削減にも貢献する。 The present invention further relates to a self-lubricating component to which the coating of the above-described embodiment is applied at least in part. In the self-lubricating part according to the invention, the coating is preferably applied to the surface of the electrical contact and provides good contact contact with a thinner layer because the wear resistance is enhanced by the coating according to the invention. This contributes to the miniaturization and simplification of the corresponding contact, and also contributes to the reduction in weight and the consumption of raw materials.
コーティングは、プラグおよびその他の接続部品、特に、プラグイン接続部分またはプレスイン接続部分に特に適する。 The coating is particularly suitable for plugs and other connecting parts, in particular plug-in connection parts or press-in connection parts.
本発明について、以下図面を参照しながら例示的実施形態に基づいて詳しく説明する。 The present invention will be described in detail below based on exemplary embodiments with reference to the drawings.
図１には、好適な実施形態における潤滑剤１の分子が示される。潤滑剤１は、多分岐の有機化合物２、すなわち樹枝状ポリマー３からなる。 FIG. 1 shows the molecules of lubricant 1 in a preferred embodiment. The lubricant 1 is composed of a hyperbranched organic compound 2, that is, a dendritic polymer 3.
ポリマー３は、結合されるモノマーの構成単位４からなり、有機化合物２として樹枝状ポリマー３を形成する著しく分岐した構造で結合する。 The polymer 3 is composed of the constituent units 4 of the monomers to be bonded, and binds in a highly branched structure that forms the dendritic polymer 3 as the organic compound 2.
本実施形態に示される樹枝状ポリマー３は、三次元においてほぼ球形の分子構造のマクロ分子有機化合物２である。この有機潤滑化合物２の空間次元は、ナノスケールの領域である。図示される球形の化合物２の空間次元ｄは、１０ｎｍより小さく、好適には３ｎｍよりも小さい。 The dendritic polymer 3 shown in this embodiment is a macromolecular organic compound 2 having a substantially spherical molecular structure in three dimensions. The spatial dimension of the organic lubricating compound 2 is a nanoscale region. The spatial dimension d of the illustrated spherical compound 2 is smaller than 10 nm, preferably smaller than 3 nm.
官能基５は、本実施形態ではチオール基６として示され、有機化合物２の表面に配置される。チオール基６は、好適には端部にモノマー単位で配置される。すなわち、端部モノマー４は、好適には構造において樹枝状ポリマー３の表面に配置される。 The functional group 5 is shown as a thiol group 6 in this embodiment, and is disposed on the surface of the organic compound 2. The thiol group 6 is preferably arranged in monomer units at the ends. That is, the end monomer 4 is preferably arranged on the surface of the dendritic polymer 3 in structure.
本発明において、図１に示される潤滑剤１は、機能活性されたナノスケール有機潤滑化合物２からなり、ポリマー３の化学的構造および物理的大きさによって、良好な潤滑特性を有し、摩耗によって解放されるコーティング７の金属層８中に潤滑剤１として効率的に埋め込まれる。 In the present invention, the lubricant 1 shown in FIG. 1 is composed of a functionally activated nanoscale organic lubricating compound 2, which has good lubricating properties depending on the chemical structure and physical size of the polymer 3, It is efficiently embedded as lubricant 1 in the metal layer 8 of the coating 7 to be released.
本発明の図１に示される好適な潤滑剤１を備える自己潤滑性コーティング７を生産するために、潤滑分子（すなわち有機化合物２）は、図２に概略図として示されるコーティング電解質１０を生産するために、イオンまたは錯体として溶解した金属９を含む電解質溶液へ加えられる。 In order to produce a self-lubricating coating 7 with the preferred lubricant 1 shown in FIG. 1 of the present invention, a lubricating molecule (ie, organic compound 2) produces a coating electrolyte 10 shown schematically in FIG. Therefore, it is added to the electrolyte solution containing the metal 9 dissolved as an ion or complex.
コーティング電解質１０は、少なくとも１種の金属イオンと、本発明の少なくとも１本は分岐している有機化合物２からなる少なくとも１種の潤滑剤１とを含む。図２には、例示的な概略図として、本発明のコーティング電解質１０が示される。特に潤滑剤１に対する金属イオン９の混合比は、任意に選択され、潤滑剤１がコーティング７に含まれる割合とは通常ならない。 The coating electrolyte 10 comprises at least one metal ion and at least one lubricant 1 comprising at least one organic compound 2 which is branched in the present invention. In FIG. 2, the coating electrolyte 10 of the present invention is shown as an exemplary schematic. In particular, the mixing ratio of the metal ions 9 to the lubricant 1 is arbitrarily selected, and is not usually the ratio in which the lubricant 1 is contained in the coating 7.
本発明のコーティング７を生産するために、電解質１０中の金属イオン９は、部品１１に付着され、潤滑分子１も金属層８中に埋め込まれる。この共同的な付着と埋め込みは、好適には電気化学的に行われ、金属イオン９は、金属原子９’からなる金属層８としてコーティングされるように表面１２上で結晶化する。この結晶化中に、潤滑分子１は、金属層８中に埋め込まれ、すなわち、金属層中に配置され。ゆえに、図３に示されるような本発明の複合コーティング７が生産される。 In order to produce the coating 7 according to the invention, the metal ions 9 in the electrolyte 10 are attached to the part 11 and the lubricating molecules 1 are also embedded in the metal layer 8. This joint deposition and embedding is preferably performed electrochemically, and the metal ions 9 crystallize on the surface 12 so that they are coated as a metal layer 8 consisting of metal atoms 9 '. During this crystallization, the lubricating molecules 1 are embedded in the metal layer 8, i.e. arranged in the metal layer. Therefore, a composite coating 7 of the present invention as shown in FIG. 3 is produced.
金属層８中に潤滑剤１を埋め込むことは、例えばチオール基６などの金属層８（特に金属層８が金または銀を含む場合）に親和性のある有機化合物２の官能基５によって促進される。 Embedding the lubricant 1 in the metal layer 8 is facilitated by the functional group 5 of the organic compound 2 having an affinity for the metal layer 8 such as the thiol group 6 (particularly when the metal layer 8 contains gold or silver). The
図３に示される実施形態において、本発明のコーティング７は、電気コンタクト１１’の表面１２に塗布される。本発明における自己潤滑性部品１１は、このようにして得られる。コーティング７は、摩耗しても、潤滑剤１が部分的にコーティング７の表面に露出して接触領域１３において潤滑膜１４を形成するので、部品１１の表面１２のより高い摩耗抵抗を確保する。 In the embodiment shown in FIG. 3, the coating 7 of the present invention is applied to the surface 12 of the electrical contact 11 '. The self-lubricating part 11 according to the present invention is thus obtained. Even if the coating 7 is worn, the lubricant 1 is partially exposed on the surface of the coating 7 to form the lubricating film 14 in the contact region 13, thereby ensuring a higher wear resistance of the surface 12 of the part 11.
上記は、接続部１５、例えばプラグイン接続部１５ａおよびプレスイン接続部１５ｂを示す図４に特に明確に示されており、２つの部品１１が、接続部１５で互いに嵌合し、各部品それぞれが接続領域１３において表面１２に本発明のコーティング７を備えている。 The above is particularly clearly shown in FIG. 4 which shows a connection part 15, for example a plug-in connection part 15a and a press-in connection part 15b, in which two parts 11 are fitted together in the connection part 15 and each part is Is provided with a coating 7 according to the invention on the surface 12 in the connection region 13.
図４には、部品１１が互いに接続部１５で接続する際において、コーティング７のそれぞれの表面１２において摩耗によって、本発明の有機化合物２の個々の分子が解放され、コンタクト領域１３に潤滑膜１４を形成する様子が示される。潤滑膜１４は、潤滑剤１（潤滑膜１４を形成する有機潤滑化合物２）の良好な摩耗特性によって、接続１５の摩耗抵抗を増加させるので、ひいては、金属層８の摩耗が著しく減少し、部品１１の摩耗抵抗も増加する。 In FIG. 4, when the components 11 are connected to each other at the connection 15, the individual molecules of the organic compound 2 of the present invention are released by wear on the respective surfaces 12 of the coating 7, and the lubricating film 14 is formed in the contact region 13. Is shown. The lubricating film 14 increases the wear resistance of the connection 15 due to the good wear characteristics of the lubricant 1 (the organic lubricating compound 2 forming the lubricating film 14), so that the wear of the metal layer 8 is remarkably reduced, and the component 11 wear resistance also increases.
本発明の例示的な実施形態では、１種類の潤滑剤しか用いられていないが、少なくとも１本の分岐を有する有機化合物２からなる異なる潤滑剤であれば、勿論異なる潤滑剤がコーティング７の金属層中に埋め込まれてもよい。 In the exemplary embodiment of the present invention, only one type of lubricant is used, but of course, different lubricants can be used for the metal of coating 7 as long as they are different lubricants comprising organic compound 2 having at least one branch. It may be embedded in the layer.
１・・・潤滑剤
２・・・有機（潤滑）化合物
３・・・樹枝状ポリマー
５・・・官能基
６・・・チオール基
７・・・コーティング
８・・・金属層
９・・・金属
１０・・・コーティング電解質
１１・・・部品
１１’・・・電気コンタクト
１２・・・スナップ部材
１５ａ・・・プラグイン接続
１５ｂ・・・プレスイン接続
DESCRIPTION OF SYMBOLS 1 ... Lubricant 2 ... Organic (lubricant) compound 3 ... Dendritic polymer 5 ... Functional group 6 ... Thiol group 7 ... Coating 8 ... Metal layer 9 ... Metal DESCRIPTION OF SYMBOLS 10 ... Coating electrolyte 11 ... Component 11 '... Electrical contact 12 ... Snap member 15a ... Plug-in connection 15b ... Press-in connection
Claims (8)
前記潤滑剤が、少なくとも１つが分岐した有機化合物（２）からなり、
前記有機化合物はマクロ分子であり、
前記有機化合物はチオール基（６）を備え、
前記有機化合物は、１０ｎｍまでの最大空間次元（ｄ）を有することを特徴とするコーティング。 A coating (7) composed of a metal layer (8) embedded with a lubricant (1) releasable by wear,
The lubricant comprises an organic compound (2) at least one of which is branched;
The organic compound is a macromolecule;
The organic compound has a thiol group (6),
The organic compound coating, wherein Rukoto which have a maximum spatial dimension (d) up to 10 nm.
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| PCT/EP2010/061125 WO2011015531A2 (en) | 2009-08-06 | 2010-07-30 | Self-lubricating coating and method for producing a self-lubricating coating |
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| FR2887256B1 (en) * | 2005-06-15 | 2010-04-30 | Rhodia Chimie Sa | DRILLING FLUID COMPRISING A POLYMER AND USE OF THE POLYMER IN A DRILLING FLUID |
| DE102005060783A1 (en) * | 2005-12-16 | 2007-06-28 | Basf Ag | Highly functional, hyperbranched polymers and a process for their preparation |
| JP5250937B2 (en) * | 2006-02-28 | 2013-07-31 | 富士通株式会社 | Lubricant, magnetic recording medium and head slider |
| CN101191244A (en) * | 2006-11-23 | 2008-06-04 | 天津市瀚隆镀锌有限公司 | Technique for producing alkaline zincate galvanizing additive |
| US7906214B2 (en) * | 2007-01-26 | 2011-03-15 | Transitions Optical, Inc. | Optical elements comprising compatiblizing coatings and methods of making the same |
| JP5019591B2 (en) * | 2007-03-29 | 2012-09-05 | 古河電気工業株式会社 | Plating material having lubricating particles, method for producing the same, and electric / electronic component using the same |
| DE102007017380A1 (en) * | 2007-04-05 | 2008-10-09 | Freie Universität Berlin | Material system and method for its production |
| WO2009034446A2 (en) | 2007-09-12 | 2009-03-19 | Australia Diamonds Limited | A method of assembly of two components |
| TR201816579T4 (en) * | 2007-12-11 | 2018-11-21 | Macdermid Enthone Inc | Electrolytic deposition of metal-based composite coatings containing nanoparticles. |
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| AR078092A1 (en) | 2011-10-12 |
| RU2542189C2 (en) | 2015-02-20 |
| BR112012002640A2 (en) | 2018-03-13 |
| MX336028B (en) | 2016-01-07 |
| EP2462261B1 (en) | 2016-05-25 |
| KR20120081083A (en) | 2012-07-18 |
| MX2012001526A (en) | 2012-03-07 |
| IN2012DN01883A (en) | 2015-08-21 |
| WO2011015531A3 (en) | 2011-05-05 |
| RU2012108146A (en) | 2013-09-20 |
| CN102471917A (en) | 2012-05-23 |
| EP2462261A2 (en) | 2012-06-13 |
| DE102009036311A1 (en) | 2011-02-17 |
| US20120129740A1 (en) | 2012-05-24 |
| JP2013501145A (en) | 2013-01-10 |
| TW201122091A (en) | 2011-07-01 |
| US9057142B2 (en) | 2015-06-16 |
| WO2011015531A2 (en) | 2011-02-10 |
| KR101710114B1 (en) | 2017-02-24 |
| TWI500758B (en) | 2015-09-21 |
| ES2587404T3 (en) | 2016-10-24 |
| CN102471917B (en) | 2015-11-25 |
| DE102009036311B4 (en) | 2021-10-28 |
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